Polyether-substituted imide compounds and their use

ABSTRACT

The present invention relates to novel polyether-substituted compounds of imides and their use as surface-active agents.

This application is a continuation-in-part of Ser. No. 08/150,722, filed Nov. 12, 1993, now U.S. Pat. No. 5,414,120.

The present invention relates to novel polyether-substituted compounds of imides and their use as surface-active agents.

Polyether surfactants containing perfluoroalkyl groups have many applications in industry due to their high surface activity. Typical applications are the improvement of flow-out and wetting properties in lacquers and dispersion adhesives or in dishwashing or cleaning agents (c.f. H. G. Klein, J. N. Meuβdoerffer and K. Niederpr um, Metalloberfl ache 29 (1975) 559 to 567). Examples of such compounds are:

C₈ F₁₇ SO₂ N(CH₃)CO--(O--CH₂ --CH₂)₅.67 --OC₄ H₉

C₈ F₁₇ SO₂ N(C₂ H₅)--(O--CH₂ --CH₂)₅ --OH

C₈ F₁₇ SO₂ N(CH₃)CO--(O--CH₂ --CH₂)₁₀.3 --OC₄ H₉

C₈ F₁₇ SO₂ N(C₂ H₅)--(O--CH₂ CH₂)₁₁₋₁₄ OH

C₈ H₁₇ SO₂ N(CH₃)CO--(O--CH₂ --CH₂)₁₉.5 --OC₄ H₉

C₈ H₁₇ SO₂ N(CH₃)CO--(O--CH₂ --CH₂)₁₄ --(OCH[CH₃ ]--CH₂)₁₄ --OC₄ H₉

Synthetic pathways to the above-stated compounds are described inter alia in DE-B 1 140 188 and in the article by H. G. Klein, J. N. Meuβdoerffer and K. Niederpr um, in Metalloberfl ache 29 (1975) 559 to 567.

Production of the perfluorinated starting compounds from the above-stated compounds proceeds according to three different synthetic pathways:

a) electrochemical fluorination,

b) telomerisation of perfluoroolefines, in particular tetrafluoroethylene,

c) oligomerisation of tetrafluoroethylene.

Since the stated methods for the production of perfluorinated starting compounds are technically very involved, production of the desired chemical compounds containing perfluoro groups is costly.

Production of the above-stated polyether surfactants containing perfluoro groups customarily proceeds by multi-stage synthesis via the reaction of perfluoroalkylsulphone amides with

a) phosgenated polyethers or

b) ethylene oxide or propylene oxide.

Such processes are described, for example, in Ullmann, Enzyklop adie der technischen Chemie, 4th edition 1982, volume 22, pages 455 to 515 and in H. G. Klein, J. N. Meuβdoerffer, H. Niederpr um and M. Wechsberg, Metalloberfl ache 29 (1975) 559 to 567. The disadvantage of these processes is that they are very involved.

The object of the invention was therefore to provide polyether surfactants containing fluoro groups, which may be used as surface-active agents and which may be produced simply and at low cost.

This object could be achieved by the polyether-substituted imide compounds according to the invention.

The invention provides imide compounds containing fluoroalkyl and/or fluoroaryl groups, which compounds are of the general formula (I) ##STR1## wherein R_(F) is a linear or branched fluoroalkyl residue with 1 to 18 carbon atoms, a fluoroaryl residue with 6 to 12 carbon atoms, a mixed fluoroalkylaryl residue with 7 to 18 carbon atoms or a fluorinated mono or polyether with 2 to 18 carbon atoms,

R is a linear or branched alkyl residue with 1 to 24 carbon atoms, an aryl residue with 6 to 12 carbon atoms or a mixed alkylaryl residue with 7 to 24 carbon atoms, wherein the carbon chain may also be interrupted by oxygen, nitrogen or sulphur atoms, or a further residue R_(F) as defined above, wherein the two R_(F) residues may be the same or different,

Y₁ and Y₂ mutually independently represent a ##STR2## m represents an integer (between) from 0 (and) to 6, n represents an integer (between) from 0 (and) to 6 and

PE represents a polyether chain consisting of 5 to 50 ethylene oxide units or 5 to 50 propylene oxide units or a mixture of 5 to 50 ethylene oxide and propylene oxide units and

R_(H) is a hydrogen atom or a linear or branched alkyl residue with 1 to 10 carbon atoms.

Imide compounds containing fluoroalkyl and/or fluoroaryl groups are preferably those in which R_(F) is a linear or branched fluoroalkyl residue with 3 to 10 carbon atoms or a fluoroaryl residue with 6 to 12 carbon atoms.

Those imide compounds containing fluoroalkyl and/or fluoroaryl groups are preferred in which R_(F) stands for a linear or branched perfluoroalkyl residue with 3 to 10 carbon atoms or for a perfluoroaryl residue with 6 to 12 carbon atoms.

Particularly preferred are those imide compounds in which R stands for a linear or branched alkyl residue with 6 to 14 carbon atoms, an aryl residue with 6 to 12 carbon atoms, a mixed alkylaryl residue with 7 to 14 carbon atoms or a linear or branched perfluoroalkyl residue with 3 to 10 carbon atoms.

Particularly preferred are those imide compounds in which Y₁ and Y₂ mutually independently stand for a ##STR3##

Imide compounds in which m and n are 0 are particularly preferred.

Linear alkyl residues with 2 to 4 carbon atoms are preferably used as terminal R_(H) groups.

Particularly preferred imide compounds exhibit, for example, the following structures: ##STR4##

The imide compounds according to the invention may be produced by reacting aminated polyethers with

fluorocarboxylic adds

fluorosulphonic acids

fluorocarboxylic or fluorosulphonic acid derivatives

and optionally with

carboxylic acids

sulphonic acids

carboxylic or sulphonic acid derivatives.

A possible synthetic pathway is reproduced below by way of example: ##STR5## wherein R_(F), R, Y₁, Y₂, m, n, PE and R_(H) have the same meaning as above and

A₁ and A₂ are mutually independently reactive leaving groups such as, for example, a halogen atom, a hydroxy, alkoxy or carboxy group.

The following starting compounds may be used for the above-mentioned process:

Examples of fluorocarboxylic acids:

    __________________________________________________________________________     perfluoroheptanoic acid                                                                           CF.sub.3 --(CF.sub.2).sub.5 --COOH                          perfluorooctanoic acid                                                                            CF.sub.3 --(CF.sub.2).sub.6 --COOH                          perfluorononanoic acid                                                                            CF.sub.3 --(CF.sub.2).sub.7 --COOH                          perfluoroethercarboxylic acid dimer                                                               CF.sub.3 --(CF.sub.2).sub.2 --O--CF(CF.sub.3)--COOH         perfluoroethercarboxylic acid trimer                                                              CF.sub.3 --CF.sub.2 --[CF.sub.2 --O--CF(CF.sub.3)].sub.                        2 --COOH                                                    perfluoroethercarboxylic acid tetramer                                                            CF.sub.3 --CF.sub.2 --[CF.sub.2 --O--CF(CF.sub.3)].sub.                        3 --COOH                                                    perfluorobenzoic acid                                                                             C.sub.6 H.sub.5 --COOH                                      2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-                                                             H(CF.sub.2).sub.6 --COOH                                    heptanoic acid                                                                 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-                                                          CF.sub.3 --(CF.sub.2).sub.5 (CH.sub.2).sub.2 --COOH         nonanoic acid                                                                  4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11 -                                                          CF.sub.3 --(CF.sub.2).sub.7 (CH.sub.2).sub.2 COOH           heptadecafluoroundecanoic acid                                                 2-tetrafluoroethoxyethanoic acid                                                                  H(CF.sub.2).sub.2 --O--CH.sub.2 --COOH                      2-hexafluoropropoxyethanoic acid                                                                  CF.sub.3 --CHF--CF.sub.2 --O--CH.sub.2 --COOH               __________________________________________________________________________

Examples of fluorosulphonic acids:

    ______________________________________                                         perfluorobutanesulphonic acid                                                                      CF.sub.3 --(CF.sub.2).sub.3 --SO.sub.3 H                   perfluorohexanesulphonic acid                                                                      CF.sub.3 --(CF.sub.2).sub.5 --SO.sub.3 H                   perfluorooctanesulphonic acid                                                                      CF.sub.3 --(CF.sub.2).sub.7 --SO.sub.3 H                   perfluorobenzenesulphonic acid                                                                     C.sub.6 F.sub.5 --SO.sub.3 H                               perfluorotoluenesulphonic acid                                                                     CF.sub.3 --C.sub.6 F.sub.4 --SO.sub.3 H                    ______________________________________                                    

Examples of fluorosulphonic or fluorocarboxylic acid derivatives:

    ______________________________________                                         perfluorobutanoic anhydride                                                                          [CF.sub.3 (CF.sub.2).sub.2 CO].sub.2 O                   perfluorobutanoic acid chloride                                                                      CF.sub.3 (CF.sub.2).sub.2 COCl                           perfluorobutanoic acid ethyl ester                                                                   CF.sub.3 (CF.sub.2).sub.2 COOC.sub.2 H.sub.5             perfluorobutanesulphonic acid fluoride                                                               CF.sub.3 (CF.sub.2).sub.3 SO.sub.2 F                     perfluorohexanesulphonic acid fluoride                                                               CF.sub.3 (CF.sub.2).sub.5 SO.sub.2 F                     perfluorooctanesulphonic acid fluoride                                                               CF.sub.3 (CF.sub.2).sub.7 SO.sub.2 F                     perfluorobenzoic acid chloride                                                                       C.sub.6 F.sub.5 COCl                                     perfluorobenzenesulphonic acid chloride                                                              C.sub.6 F.sub.5 SO.sub.2 Cl                              ______________________________________                                    

Examples of carboxylic acids:

    ______________________________________                                         n-butanoic acid  CH.sub.3 CH.sub.2 CH.sub.2 COOH                               n-pentanoic acid CH.sub.3 (CH.sub.2).sub.3 COOH                                n-hexanoic acid  CH.sub.3 (CH.sub.2).sub.4 COOH                                n-heptanoic acid CH.sub.3 (CH.sub.2).sub.5 COOH                                n-octanoic acid  CH.sub.3 (CH.sub.2).sub.6 COOH                                n-nonanoic acid  CH.sub.3 (CH.sub.2).sub.7 COOH                                n-decanoic acid  CH.sub.3 (CH.sub.2).sub.8 COOH                                n-undecanoic acid                                                                               CH.sub.3 (CH.sub.2).sub.9 COOH                                n-dodecanoic acid                                                                               CH.sub.3 (CH.sub.2).sub.10 COOH                               2-methylpropanoic acid                                                                          (CH.sub.3).sub.2 CH--COOH                                     3-methylbutanoic acid                                                                           (CH.sub.3).sub.2 CH--CH.sub.2 COOH                            2,2-dimethylpropanoic acid                                                                      (CH.sub.3).sub.3 C--COOH                                      2-methylbutanoic acid                                                                           CH.sub.3 CH.sub.2 CH(CH.sub.3)--COOH                          2-ethylbutanoic acid                                                                            CH.sub.2 CH.sub.2 CH(C.sub.2 H.sub.5)--COOH                   2-ethylhexanoic acid                                                                            CH.sub.3 (CH.sub.2).sub.3 CH(C.sub.2 H.sub.5)--COOH           isomeric C.sub.8 acids                                                                          C.sub.7 H.sub.15 COOH                                         isomeric C.sub.9 acids                                                                          C.sub.8 H.sub.17 COOH                                         isomeric C.sub.13 acids                                                                         C.sub.12 H.sub.25 COOH                                        nonadecanoic acid                                                                               C.sub.18 H.sub.37 COOH                                        cyclohexanecarboxylic acid                                                                      C.sub.6 H.sub.11 COOH                                         propenoic acid   CH.sub.2 ═CH--COOH                                        2-methylpropenoic acid                                                                          CH.sub.2 ═C(CH.sub.3)--COOH                               trans-3-methylpropenoic acid                                                                    CH.sub.3 CH═CH--COOH                                      cis-3-methylpropenoic acid                                                                      CH.sub.3 CH═CH--COOH                                      2,3-dimethylpropenoic acid                                                                      CH.sub.3 CH═C(CH.sub.3)--COOH                             hexane diene carboxylic acid                                                                    CH.sub.3 CH═CHCH═CH--COOH                             11-undecenoic acid                                                                              CH.sub.2 ═CH(CH.sub.2).sub.8 COOH                         acetylenic acid  CH.tbd.C--COOH                                                benzoic acid     C.sub.6 H.sub.5 --COOH                                        methylbenzoic acid                                                                              CH.sub.3 C.sub.6 H.sub.4 --COOH                               phenylacetic acid                                                                               C.sub.6 H.sub.5 CH.sub.2 --COOH                               naphthylacetic acid                                                                             C.sub.10 H.sub.7 --CH.sub.2 --COOH                            ______________________________________                                    

Examples of sulphonic acids:

    ______________________________________                                         methanesulphonic acid                                                                           CH.sub.3 SO.sub.3 H                                           ethanesulphonic acid                                                                            CH.sub.3 CH.sub.2 SO.sub.3 H                                  propanesulphonic acid                                                                           CH.sub.3 (CH.sub.2).sub.2 SO.sub.3 H                          butanesulphonic acid                                                                            CH.sub.3 (CH.sub.2).sub.3 SO.sub.3 H                          pentanesulphonic acid                                                                           CH.sub.3 (CH.sub.2).sub.4 SO.sub.3 H                          hexanesulphonic acid                                                                            CH.sub.3 (CH.sub.2).sub.5 SO.sub.3 H                          vinylsulphonic acid                                                                             CH.sub.2 ═CHSO.sub.3 H                                    methallylsulphonic acid                                                                         CH.sub.2 ═C(CH.sub.3)--CH.sub.2 --SO.sub.3 H              benzenesulphonic acid                                                                           C.sub.6 H.sub.5 SO.sub.3 H                                    toluenesulphonic acid                                                                           CH.sub.3 C.sub.6 H.sub.4 SO.sub.3 H                           ______________________________________                                    

Examples of sulphonic or carboxylic acid derivatives:

sulphonic/carboxylic acid halides

sulphonic/carboxylic acid esters

sulphonic/carboxylic anhydrides

sulphonic/carboxylic acid salts.

The invention also provides the use of the imides according to the invention and their salts as surface-active agents.

Due to the high surface activity of the imide compounds according to the invention, the imide compounds may, for example, be used in the following fields of application:

In electrolytic processes (for example in electroplating with chromium, copper and nickel, in anodising and in electrolytic degreasing), the compounds according to the invention may be added to suppress spray mist and to prevent discharge losses.

In non-electrolytic bath processes (for example in chemical copper or nickel plating, in chemical degreasing or rust removal, in etching or engraving, in bright dipping, in pickling, black finishing or passivation, in anodic oxidation or in deplating), the compounds according to the invention may be added as spray mist suppressants and cleaning auxiliaries.

In cleaning and maintenance products (such as, for example, in glass, oven, car, building, cladding or metal surface cleaners, in stain removers, in shampoos, in polishes for furniture, cars etc., in self-polishing emulsions or in waxes), the compounds according to the invention may be added as flow control, spreading and wetting agents and to support the properties preventing soil redeposition.

The compounds according to the invention may be used as they are or in formulations as anti-fogging or anti-tarnishing agents (for example for glass, metals or plastics).

The compounds according to the invention may be used as they are or in formulations as corrosion inhibitors or corrosion-protective coatings (for example in polymerisation reactions, for fillers, fibres, salts or magnetic solids, in lacquers or in blood replacements).

Due to their tendency to form gastight barrier layers and therefore to prevent the evaporation or vaporisation of liquids, the compounds according to the invention are also suitable as additives to fire-extinguishing agents.

The compounds according to the invention may be used as mould release agents.

In paints and lacquers, addition of the compounds according to the invention improves flow-out, wetting and adhesion properties. Moreover, by promoting deaeration, they prevent the formation of surface defects (such as, for example, cratering or running-away). Furthermore, adding them improves pigment distribution. The non foam-stabilising action of the compounds according to the invention is particularly advantageous in formulations in the production of water-thinnable lacquers.

The tendency of the compounds according to the invention to form hydrophobic and oleophobic barrier layers makes their use possible in architectural protective agents (for example to screen from environmental influences).

The compounds according to the invention may be used as flow or slip agents (for example in mineral ores or salts, on magnetic tapes or in building materials).

The compounds according to the invention are suitable as lubricants, cutting oil additives or hydraulic oils.

The compounds according to the inventions may be used as drilling auxiliaries (for example increased performance in oil drilling).

The compounds according to the inventions may be used in photographic chemicals or in film production (for example as wetting or anti-static agents).

The compounds according to the invention may be used in plant protection products (for example as wetting and flow control agents).

Addition of the compounds according to the invention to finishes for textiles, leather or paper may, for example, promote wetting or penetration of the finish, provide a defoaming effect or support the finish's hydrophobic/oleophobic action.

The invention is more closely illustrated with the following examples.

EXAMPLES Example 1

0.3 mol (273.9 g) of polyether of the formula H₂ N(CH₂ CH₂ O)₁₉.6 C₄ H₉ and 0.3 mol (30.3 g) of triethylamine are heated to 50° C. in a three-necked flask with stirrer, 0.3 mol (150.6 g) of perfluorooctylsulphonyl fluoride are added over 15 minutes and the mixture refluxed for 4 h 30 min while being stirred.

After cooling, a further 0.3 mol (30.3 g) of triethylamine are added, the mixture heated to 50° C., 0.3 mol (90.6 g) of perfluorobutylsulphonyl fluoride added over 15 minutes and refluxed for 2 h while being stirred.

Yield of the desired N-perfluorobutylsulphone-N-perfluorooctylsulphone imide compound is 491 g (corresponding to 98% of theoretical). The surface tension of a 0.1% aqueous solution is 28.1 mN/m, that of a corresponding 1% solution 26.0 mN/m (measured with a ring tensiometer from Lauda).

Example 2

0.3 mol (273.9 g) of polyether of the formula H₂ N(CH₂ CH₂ O)₁₉.6 C₄ H₉ and 0.6 mol (60.6 g) of triethylamine are heated to 50° C. in a three-necked flask with stirrer, 0.6 mol (181.2 g)of perfluorobutylsulphonyl fluoride are added over 15 minutes and the mixture refluxed for 10 h while being stirred.

Yield of the desired bis-perfluorobutylsulphone imide compound is 421 g (corresponding to 95% of theoretical). The surface tension of a 0.1% aqueous solution is 36.6 mN/m, that of a corresponding 1% solution 26.5 mN/m (measured with a ring tensiometer from Lauda).

Example 3

0.3 mol (273.9 g) of polyether of the formula H₂ N(CH₂ CH₂ O)₁₉.6 C₄ H₉ and 0.3 mol (30.3 g) of triethylamine are heated to 50° C. in a three-necked flask with stirrer, 0.3 mol (90.6 g) of perfluorobutylsulphonyl fluoride are added over 15 minutes and the mixture refluxed for 2 h while being stirred.

After cooling, a further 0.3 mol (30.3 g) of triethylamine are added, the mixture heated to 50° C., 0.3 mol (58.8 g) of octylsulphonyl fluoride added over 15 minutes and refluxed for 24 h while being stirred.

After cooling, the mixture is washed with 150 ml of water and dried at 40° C. and 50 mbar. Yield of the desired N-perfluorobutylsulphone-N-octylsulphone imide compound is 276 g (corresponding to 67% of theoretical). The surface tension of a 0.1% aqueous solution is 41.6 mN/m, that of a corresponding 1% solution 30.7 mN/m (measured with a ring tensiometer from Lauda).

Example 4

0.05 mol (53.20 g) of polyether of the formula H₂ N (CH₂ CH₂ O)₁₉.6 C₄ H₉ and 0.05 mol (5.05 g) of triethylamine are heated to 60° C. in a three-necked flask with stirrer, 0.05 mol (19.85 g) of perfluorooctanoyl chloride are added over 37 minutes and the mixture refluxed for 12 h while being stirred.

After cooling, a further 0.05 mol (5.05 g) of triethylamine are added, the mixture heated to 60° C., 0.05 mol (6.35 g) octanoylchlorid added over 15 minutes and refluxed for 11 h while being stirred.

Yield N-perfluoroctane-N-octane imide compound is 72 g (corresponding to 98% of theoretical). The surface tension of a 0.1% aqueous solution is 31.9 mN/m, that of a corresponding 1% solution 25.2 mN/m (measured with a ring tensiometer from Lauda).

Melting Point: 30°-40 ° C.

Boiling Point: 130°-138 ° C.

Example 5

0.05 mol (53.20 g) of polyether of the formula H₂ N (CH₂ CH₂ O)₁₉.6 C₄ H₉ and 0.05 mol (5.05 g) of triethylamine are heated to 80° C. in a three-necked flask with stirrer, 0.05 mol (16.01 g) of perfluorobutylsulphonyl fluoride are added over 90 minutes and the mixture refluxed for 15 h while being stirred.

After cooling, a further 0.05 mol (5.05 g) of triethylamine are added, the mixture heated to 80° C., 0.05 mol (6.35 g) octanoylchlorid added over 8 minutes and refluxed for 11 h while being stirred.

Yield N-perfluorobutylsulphone-N-octane imide compound is 70 g (corresponding to 98% of theoretical). The surface tension of a 0.1% aqueous solution is 46.1 mN/m, that of a corresponding 1% solution 27.1 mN/m (measured with a ring tensiometer from Lauda).

Melting Point: 30°-40 ° C.

Boiling Point: 105°-110 ° C. 

What is claimed is:
 1. Imide compounds containing at least one of fluoroalkyl and fluoroaryl groups, which compounds are of the general formula (I): ##STR6## in which R_(F) is a linear or branched fluoroalkyl residue with 1 to 18 carbon atoms, a fluoroaryl residue with 6 to 12 carbon atoms, a mixed fluoroalkylaryl residue with 7 to 18 carbon atoms or a fluorinated mono or polyether with 2 to 18 carbon atoms,R is (i) a linear or branched alkyl residue with 1 to 24 carbon atoms, an aryl residue with 6 to 12 carbon atoms or a mixed alkylaryl residue with 7 to 24 carbon atoms, wherein the carbon chain may also be interrupted by oxygen, nitrogen or sulphur atoms, or (ii) a further residue R_(F) as defined above, wherein the two R_(p) residues may be the same or different,each of Y₁ and Y₂ represent a ##STR7## or Y₁ represents a >C═O group and Y₂ represents a ##STR8## m is an integer from 0 to 6, n is an integer from 0 to 6 and PE is a polyether chain consisting of 5 to 50 ethylene oxide units or 5 to 50 propylene oxide units or a mixture of 5 to 50 ethylene oxide and propylene oxide units and R_(H) is a hydrogen atom or a linear or branched alkyl residue with 1 to 10 carbon atoms.
 2. Imide compounds containing at least one of fluoroalkyl and fluoroaryl groups according to claim 1, wherein R_(F) is a linear or branched fluoroalkyl residue with 3 to 10 carbon atoms or a fluoroaryl residue with 6 to 12 carbon atoms.
 3. Imide compounds containing at least-one of fluoroalkyl and fluoroaryl groups according to claim 1, wherein R_(F) is a linear or branched perfluoroalkyl residue with 3 to 10 carbon atoms or a perfluoroaryl residue with 6 to 12 carbon atoms.
 4. Imide compounds according to claim 1, wherein R is a linear or branched alkyl residue with 6 to 14 carbon atoms, an aryl residue with 6 to 12 carbon atoms, a mixed alkylaryl residue with 7 to 14 carbon atoms or a linear or branched perfluoroalkyl residue with 3 to 10 carbon atoms.
 5. Imide compounds according to claim 1, wherein m and n are O.
 6. Imide compounds according to claim 1, wherein R_(H) is a linear alkyl residue with 2 to 4 carbon atoms. 